Diels-alder condensation products of certain polyolefinic, cyclic hydrocarbon fractions



Patented July 11, 1950 DIEL'S-AI JDER CONDENSATION PRODU-CTS OF CERTAIN POLYOLEFINIC, CYCL'IC- HY- DROCARBON FRACTIONS HermanS. Bloch, Chicago, Ill., a'ssignor 'to Universal Oil Products Company; Chicago, 111., a

corporation of Delaware No Drawing. Application December 24,4947, Serial No. 793,764

4 Claims. (01. 260468) This application is a continuation in part of my co-pending application Serial No. 561,324, filed October 31; 1944, now abandoned.

The present invention relatestonew surface active. agents having washing, wetting and emulsifying activity and'to aprocess for the manufacture of such materials. More particularly, the present process concernsthe production of said surface active agents "from a particular charging stock of specified'origin'as hereinafter provided.

An object of my invention is to prepare watersoluble salts o'fa new classnf'acidic compounds.

A further object of myinventi'on is to provide a .process for the manufacture of "new wetting agents anddetergen'ts.

Still another object of "the present processis to provide an economical "source "of highly effectivesur'face active agents derived from'a class of conjugated polyole'finic hydrocarbons'having a cyclic structure in'which a portion "ofthe unsaturation is 'intra cyclic' and a portion thereof is extra-cyclic.

Whencertain types of hydrocarbons, generally characterized "as non-aromatic, unsaturated types, "are reacted-in "the presence of catalysts capable of promoting conjunct polymerization reactions, under carefully controlled conditions of reaction; the'spent catalyst phase is found" to contain "valuable hydrocarbonaceous substances of 'polyeolefinicycyclic structure having --a'h'igh degree cf conjugated unsaturation. This material which ---can be recovered from the catalyst phase, 'as hereinafter set forth, isreferred to in the aggregate as 'amixture of conjunct polymers. It is believed that the hydrocarbon conjunct polymers present in the-spent catalyst phase and recovered therefrom by special methods of treating thesameare combined with the catalyst in the form of loosely bound complex addition compounds'yvhichare decomposed-during the treatment "for the recovery of the hydrocarboncomponen't thereof.

Broadly, this-invention relates: tosurface active salts of acids 'prepared by reacting an acidic dienophile w-ithsaid conjunct polymers containing a major proportionof polyolefinic, cyclic hydrocarbons having :a-- high degree of. conjugated .unsaturation.

In' one .of its more specific embodiments, the present invention relates tothe production of surface: active agents comprising the neutral salts of :dienophilic acidic adducts, prepared by reactingamono-or. polybasic acidic 'dienophile with the mixtureuof conju-nct:polymers= obtained upon decomposition of a catalyst-hydrocarbon conjunct polymerization sludgeand' neutralizing said adduct with 'a-"basic" neutralizing agent to form a water soluble salt'th'ereof.

lIn 'ac'cordance'with another embodiment of the presentinvention, a surface-active 'agentis prepared'by'reacting 1a dibasic acidic *dienophile with a' fraction boiling from about 275 to about 375 C. of 'conjunct "hydrocarbon "polymers recovered "by "hydrolysis of "'a hydrogen fluoride sludge; 'theindividua-l hydrocarbonsof which contain from'iabout 16' to -about 27' carbon atoms per molecule, thereafterseparating the acidic adduct from the reactionmixture-arid neutralizing the same-"with sodiumhydroxi'de to form a Water soluble salt thereof comprising said detergent.

The mixture of unsaturated cyclic hydrocarbons herein referred "to as con-junct polymers utilizedas one of the -primaryreactants in the formation of the present surface active agents. is the product of the so-called conjunct polymerization reaction-referring toa series 0f successive as-well as 'simultaneous reactions occurring in a reaction "mixture comprising unsaturated, nonaromatic' hydrocarbons and a reagentspecified as a conju-n'et polymerizationcatalyst. On contacting -the"hydrocarbon starting material with the catalyst at reaction conditions "generally referred to as -sludge-forming conditions, the catalyst effects polymerization .of the hydrocarbon reactants charged-as-welLas cyclization and hydrogen transfer between the hydrocarbon reaction components. The-net result of the combined hydrogen transfer, polymerization and cyclization reactions (which, .inl effect occur substantially as a simultaneous :combination reaction referred to in the aggregateas a conjunctpolymerization reaction) .is the production of high molecular weight, unsaturated hydrocarbon molecules having. generally :a: polycyclic. structure (although the lowmolecular weightmembers are usually monocyclic) and containing numerous olefinic bonds, averagingfromabout- 2 to about 35 double bonds per molecule and in :somecomponents of themixture, being as high as 4 per molecule, of which from 4-0 to percent are conjugated. The unsaturated hydrocarbons formed as a result of the conjunct polymerization reaction combine -with the catalyst in -certain definite ratios to form a sludge-like complex from which the 'conjunct polymers. utilized as one of the primary reactants herein may be recovered. As a result of the hydrogen transfer occurring-during the conjunct polymerization reactiomsome of the hydrocarbons present in the reaction -mixture become extent upon the type of hydrocarbons employed I in the sludge-forming or conjunct polymerization 'f l reaction. Suitable hydrocarbon starting material comprises, in general, unsaturated hydrocarbons containing at least 3 carbon atoms per molecule such as olefins of either branched or straight chain structure. When utilized as a majorcomponent of the charging stock, propylene is desirably admixed with high molecular weight hydrocarbons especially olefins containing at least 6 carbon atoms per molecule, and a larger proportion of catalyst to hydrocarbons is charged to the sludge-forming reaction. Paraflinic hydrocarbons, either alone or in admixture with olefins may also form desirable sludges, especially when branched chain paraffins are selected and when slightly higher temperatures are'pr'ovided for the reaction compared to the temperature utilized for the conversion of an olefinic charge. Conjunct polymers containing an especially high degree of unsaturation may be prepared when the charging stock to the sludge-forming re-I action contains polyoleflns and/or acetylenic hy-, drocarbons containing at least 4 carbon atoms per molecule. An especially preferred charging stock from the standpoint of general availability and desirability in yielding a mixture of conjunct polymers especially suitable in the formation of the present surface active agents is an olefin polymer containing propylene and/or butylene dimers and trimers or a C6 to C12 fraction of a thermally cracked gasoline product which is low centration above about H2604, hydrogen fluoride containing at least 90% HF, preferably the substantially .anhydrous reagent, andboron trifluoride, especially in admixture with hydrogen fluoride. In general, hydrogen fluoride is preferred in the preparation of the sludge because of subsequent considerations involved in recovering the catalyst for recycling to the sludgeforming'stage of the process without destroying a large proportion of the conjugated unsaturation of the conjunct polymers as they exist within the sludge bound to the hydrogen fluoride component. a

When utilizing hydrogen fluoride as catalyst in the formation of the conjunct polymers, the reaction may be effected at temperatures of from about 30 to about 150 0. (preferably from about 0 to about C.) and the ambient pres sure is maintained sufficientlysuperatmospheric to provide substantially complete liquid phase of the reactants. In utilizing aluminum chloride, temperatures of from about 10 to about C. are preferred and with sulfuric acid, the temperature of reaction is preferably maintained slightly lower than for aluminum chloride, (from about 0 to about 100 C.) because of the oxidizing effect of sulfuric acid at higher temperatures. The reactants,,generally in'weight proportions of from about four parts of hydrocarbon stock to one part of catalyst up to corresponding values of about one to three may be employed. Intimate admixture of the reactants is desirable, so that stirring is generally employed to effect contact between thecatalyst and hydrocarbons. The reaction issubstantially complete after about onehalf'hour." v

, The sludge formed in the conjunct polymerization reaction as a lower layer reaction product thereof may be treated in accordance with several alternative procedures to recover therefrom the conjunct hydrocarbon polymers utilized as starting material in the present process to form the surface active products. One method especially utilizedin the case of aluminum chloride and sulfuric acid sludges, but also applicable to a hydrogen fluoride sludge, isby means of aqueous hydrolysis wherein the sludge is merely stirred into or admixed with water or aqueous caustic until the liberation of the conjunct polymers from the sludge is complete. The latter separate as an upper hydrocarbon layer and may be decanted from the lower aqueous layer.

Thermal decomposition of the sludge may also be employed, and this is especially adapted to hydrogen fluoride sludges, where the catalyst component is readily'vaporizable at relatively low temperatures, and may be recovered in the substantially anhydrous condition suitable for recycling to the sludge-forming reaction.

The mixture of conjunct polymers as recovered from the catalyst-hydrocarbon sludge in accordance with the methods hereinabove described comprises a series of high molecular weight cyclic compounds of wide boiling range but of homologous structure of which a large proportion contains conjugated olefinic double bond systems,

,although the exact composition of the mixture will vary somewhat depending upon the particular charging stock, the catalyst and the conditions of operation employed. I The material has a wide boiling range of from about 150 to over 450 0., density of from about 0.83 to about 0.93, index of refraction of from about 1.47 toabout 1.53 (but usually 1.48 to l.50),specific dispersion of from about 125 to about 175 (usually between and bromine numbers above about 140 (although they vary considerably with the average molecular weight), maleic anhydride values of about 30 to about 90 (usually in the range of about 45 to 75), and acid numbers below about 3.

. The conjunct polymers range in average molecular weights from about 200 to about 400, although the usual average is in the neighborhood of about 300. Certain fractions of the mixture of conjunct polymers have molecularweights of as low as about to as high as about 1000. Although hydrogen to carbon atomic ratios vary somewhat depending upon the particular source of the material, for the product derived from a hydrogen fluoride catalyst sludge they range from about 1.67 to about 1.72 (for the various fractions) with the actual percentages of hydrogen varying from about 12.35 to 12.6. The individual hydrocarbons contain a conjugated system of olefinic double bonds as well as isolated conjugation, the total number of double bonds' 1 per' molecule of hydrocarbon averaging from;

atlases s. about:.2.5 to about: 4, .:of' which irom1=abo11t40+to aboutflomercentare conjugated, dependinglupon the :molecular weight: of "the hydrocarbon: component. :Onthe'basis of analytical .data;;obtained by infra-red and ultra-violet :absorption spectra, as well as ..=chemical data, I the z low I boiling. .fractions .of the mixture of 'conjunct polymer hydrocarbons consist mostly: of, :monocyclic hydrocarbons while. the higher rboiling fractions-pf the mixture are .of :polycyclic, generally bicyclic; structure. In :bothlseries of hydrocarbons, the .cyclic portion :of the .molecule -.is a "C ring; having sattached thereto :at least 2 -alkyl:or unsaturated aliphatic tsubstituents :and .probably at least *3 such'zgroups. :The data furtherzlindicatethat one of "the v:bonds comprising the :conjugatedusystem is cvwithin the-C5 :cyclic portion .of-xthe molecule and the other double bond of the conjugatedpair resides :in one or more of-the =alkenyl 01 alkapolyenyl substituents. .Thelatter groups :orwsi'de chains are highly branched and-.may containa'isolated unsaturation as well as conjugated lunsaturation. Thexhydrocarbon components present in the mixture of conjunct polymers boil over a relatively;wide" boilingrrange ofwfrom about 1-50'1to "about .450" .C. and.:c.omprise"a;series of homologues and isomers. Typical xhydrocarbons contained in the ;:mixture .of lconjunct polymers may be .represented structurally .by the. :formula:

of the most effective agents 'of 'thistype knownp For this purpose, fractions boiling from about 275 to about 375C. are especially valuable, "said fractionscontaining components having molecular weights of from about 225 to about 380,'corresponding to carbon atom contents of "from about 16'to about'2'7 carbon 'atoms .per molecule. It is believed the latter fractions are largely'monocyclic containing relatively large branched chain aliphatic radicals attachedto the cyclic nucleus. To effect separation of'various fractions of the mixture'of conjunct polymers, it is desirable to employ *subatmospheric fractional distillation at pressures preferably less than about 50- mm; mercury absolute.

To prepare the dibasic'acidicadducts'of this invention, the neutral salts of which comprise the desired surface'active products of the present process, the above com'unct polymers, separated from a conjunct'polymerization catalyst-hydrocarbon sludge are reacted or condensed with 'a dienophilic 'monoor dibasic acidic compound. The latter class of reactantsare characterized as unsaturated-acids or=their-anhydrides containing a-, fl-olefinic unsaturation which are capableof condensing with a; conjugated 'polyenic compound to :yield :an :adduct :thereof.

enophilesscontaint'the reactive group:

mechanism involving the present reactants 'is representedby the following equation in which a 'lowermolecular weight, monocyclic conjunct polymer andamono-basic acidic dienophileare selected as the typical reactants:

where R" is a hydrogen atom, alkyl, a-lkenyl .zor polyenyl group. acidic product represents the detergent intermediate which when neutralized yields one of the'typi-cal products of thepresent invention. --Of theutilizable' acidic dienophiles in the reaction,- representati've compounds of this typeare-maleic orfumaric acid, itaconic acid, citraconic acid, crotonic acid, and acrylic acid, their-anhydrides and-esters. The dibasic acids and their anhydri-despparticularly maleic acid-and anhydride are "preferred herein because u of their general availability and the highly effective-surface active properties of their adducts and salts.

The reaction involved'in the formation of thea'dductsproceeds at temperatures generally below about'120- C.,--preferably at temperatures of from about 60 to about C. When the lower boiling fractions of the mixture of conjunct polymers are utilized as the hydrocarbon reactant, condensation may-eventake'place sponaverage molecular Weight of between about 300 and about 600 and having for the most part at least two olefinic double bonds per molecule.

The polyolefinic, polycyclic, acidic adducts herein provided, comprising the acidic predecessor of the present detergent, are preparedby commingling the mixture .ofconjunct polymers or selected fractions thereof with maleic anhydride orother dienophile and heating the mixture to atemperature of from about 86:to about 110- C., preferably under reflux, until the reaction A typical reaction.

The bicycl-ic, non-aromatic is'compl'ete. In some cases completion of'the re.- action maybe tested by determining the'diene values of recovered unreacted hydrocarbons. A

more convenient method, however, isthe method of following the reaction by the reduction in dispersion of the reaction mixture as reaction proceeds. The proportionof maleic anhydride to hydrocarbon conjunct polymers employed may be varied, depending upon the character of the hydrocarbon mixture and the desired end product, but generally, it is preferred to have present an excess of the conjunct hydrocarbon polymers in the reaction mixture to obtain a nearly complete conversion of the dienophilic acid as possible. An excess of certain dienophiles such as maleic anhydride may also be used, and the unreacted portion recovered by sublimation from the reaction mixture. The adduct acids are then converted to the sodium salt or other watersoluble salt of the type hereinabove set forth by reacting the acidic adduct with an aqueous alkali or other neutralizing agent such as sodium hydroxide, until a clear solution is obtained. This solution is then allowed to cool and in some cases finally chilled with ice. The neutralized soap usually precipitates from the cooled aqueous mixture and may thereafter be filtered, dried and recovered as a nearly white granular solid. Other salts of the adduct acids with such bases as ammonia, the mono-, di-, and trialkyl or alkanol amines, such as for example, dibutylamine and triethanol amine etc., pyridine, and the like may be prepared for specific applications. In a typical application, for-example, a wholly organic salt such as an alkylamine or alkanolamine reaction product of the adduct acids may be utilized where solubility requirements give preference to salts of this type, as, in the case of dissolving the salt in an organic solvent, such as a drying oil.

To the salts of the invention, various additives, water-softeners, or builders may be added, as for example, such material as sodium silicate, sodium borate, sodium carbonate, sodium sulfate, sodium phosphate, sodium polyphosphates, etc., particularly when the products are to be used as detergents in aqueous solutions thereof. When added to the present surface active agents to provide a detergent composition, the builder salts may comprise up to about 85% by weight thereof, preferably from 35 to about 65% by weight.

The detergents prepared according to the method hereinabove outlined are adapted to the preparation of emulsions between numerous hydrophilic and lipophilic materials. They are particularly suitable for preparing water-emulsion paints, since the unsaturated character of the acid radicals is believed to lead to their ultimate oxidation and polymerization or copolymerization with the drying oil ingredients present in the emulsion, thus, entering into the formation of a portion of the film resulting on drying the emulsion paint. In addition to being used alone as washing, wetting or emulsifying agents, the compositions of my invention may be combined with other synthetic surface active agents or with soaps derived from natural glyceride oils.

The following examples are intended to illustrate my invention, but are not to be considered as limiting the generally broad scope of the invention in strict accordance therewith.

Example I sistin-gf predominantly of. mono-olefinic hydrocarbons .containing .from'. 8 to '12 carbon atoms per'molecule'was charged into an autoclave and rapidly stirred :as 9.0 .kg; of liquid anhydrous hydrogen fluoride was introduced into the reactor. The pressure was maintained throughout the reaction at an 'average value of about 205 pounds per square inch by means of compressed nitrogen. The temperature was increased to 91 C. and stirring wascontinued for an additional 1 hour. The reaction mixture was allowed to stand quiescent for several minutes, the mixture separating into two phases on standing: an upper saturated hydrocarbon layer (bromine number-10) and a lower acidic layer. The upper layer, after washing with caustic solution to remove a small amount of dissolved hydrogen fluoride, weighed 8,1 kg, 5 1. i

The lower acidic layer weighed 16.1 leg. after removal of entrained upper layer by extracting the latter with liquid pentane and was a light brown mobilefiuid having a density of 0.98 at 4 .0. Its yield, based on the total charge, was 65.5 percent.

' The abovehydrogen fluoride sludge, when introducedinto water, decomposes violently, liberating'considerable heat, and results in the separation of an oil on the surface of the aqueous phase. In this .stage of the process, 100 g. of the coordination compound as prepared above was allowed to flow into a mixture of ice and water, additional ice being added as the heat of reaction melted the ice in the hydrolyzing reactor. 43.4 g. of a light-colored, sweet-smelling oil separated from the aqueous phase, a yield of 42. 1% based on the original olefin charged and 43.4% based on the Weight of sludge hydrolyzed. An examination of the oil indicated the following properties.

Although the conjunct polymers herein provided were prepared from a hydrogen fluoride sludge and were recovered therefrom by an aqueous hydrolysis procedure, substantially the same material may beobtained from an aluminum chloride or sulfuric 'acid sludge, as hereinabove specified and the conjunct hydrocarbon polymers may be recovered from the hydrogen fluoride sludge by distilling off the hydrogen fluoride. If

v the sludge is'subjected to excessive distillation temperatures or periods of contact with the hydrogen fluoride, however, the conjunct polymers in the sludge tend to condense into higher molecular weight compounds. containing fewer conjugated olefinic bonds.

The mixture of conjunct polymers or sludge hydrocarbons as separated by the above hydrolyzing procedure was Vacuum distilled into several fractions and adducts were prepared from each of the separate-fractions by heating the same with the theoretical molecular equivalent of the acidic, dienophile' reactant, where the molecular equivalent of the hydrocarbon reactant was based upon the average molecular weight of the -P.M. for =minutes at 140 F. (60C.).

swatches were then rinsed thoroughly in disindicated fractions 'of-conjunct polymers is given in the following table:

Maleic anhydride adduct, parts by Weight -S%urce of adduct (conjunct polymer fraction boiling range,

Molecular wei ht Sodium hydroxide, parts'by Weight, Water, parts by wei ht Weight of soap, parts by Weight .Percent sodium in soap Atoms of sodium per mol of soap Atoms of carbon per mol of soap The wetting-power ofthe-sodium soaps of the maleic anhydrideadduct-o'f certain fractions of the conjunct polymers as determined by the Draves Wetting Test are shown in the following -'tab1e:

Wagting power rams per Bggmgf i fi Molecular liter required i mct Polymers Weight s onds Draves Test The data show that the maximum wetting power is obtained with soaps derived from those fractions of the conjunct polymers having a boil- Grams per liter re quired for 25 seconds Draves Compounds sinking time at C Sodium salt of maleic anhydride adduct-. Triamylbenzene sodium sulfonate Sodium oleate Tertiary amylbenzine sodium sulfonate The detersive effect of the composition of my invention was tested as follows: 10 rubber balls diameter, each weighing about 1.1 grams) and three 2" x 2" swatches of standard soiled. cloth (soiled with a graphite, mineral oil and vegetable oil mixture) were placed in 200 m1. of

the detergent solution containing various concentrations of electrolyte (sodium sulfate) in pint jars. These were sealed and fastened to the rotor of a standard launderometer and rotated at 42 The tilled water, squeezed by hand andlaid out on towels to dry. When dry, the swatches'were read on a photovolt refiectometer. It was found-that with variousconcentrations of sodiumsulfate at 005% concentration of detergent, the cloth gave a -reflectancy-of 42with the optimum amount of sodium sulfate. When washed in plain-water, the soiled cloth gave a reflectancy of about 28. The optimum washing power isobtained with soaps derived from a conjunct polymer fractionhaving .anavera'ge'boiling .point'of fromabout320 C. .to 'about375 C. and a molecular weight .of .about260 to abouti380, corresponding to arange of about 275-320 320 370 370 3257 y 321 448 6. .62 5. 40 4. 85 I 1'64 136 170 27. 37 25224 34. 13 8..8 6. 9 5. 8 1.55 1.40 1.50 I 23 27 -37 19 to about 2'7 carbon atoms permolecule or an average of about 22.carbon atoms.

Example II Impliepare .the soapaof 'a =monobasie adduct of the conjunct polymers, thelatter hydrocarbons were heated with an equivalent amount of methylacrylate at a temperature of C. The esters were saponified and the water insoluble material recovered after conversion to the acid form. The acid material was then separated from the inert hydrocarbon, by extraction of the latter with petroleum ether from a. water solution of the sodium salts formed by neutralization of the acids. The soap of the monobasic adduct was found to foam better than did that of the soap of the maleic anhydride adduct and to have surfaceactive powers.

I claim as my invention:

1. A surface active agent comprising a water soluble salt of an adduct of, (1) an acidic dienophile selected from the group consisting of the mono and dibasic acidic compounds containing the reactive group:

lane

and (2) a polyolefinic, cyclic hydrocarbon fraction boiling in the range of from about 150 to about 450 C., and having an average molecular weight of from about 200 to about 400, an average number of olefinic bonds per molecule of from about 2.5 to about 4 of which from about 40 to about 70% are conjugated, a density of from about 0.83 to about 0.93, an index of refraction of from about 1.47 to about 1.53, a specific dispersion of from about to about 175, a bromine number above 140, a maleic anhydride value of from about 30 to about 90 and an acid number below about 3.

2. A surface active agent comprising a wate soluble salt of an adduct of, (1) maleic anhydride and (2) a polyolefinic, cyclic hydrocarbon fraction boiling in the range of from about to about 450 C., and having an average molecular weight of from about 200 to about 400, an average number of olefinic bonds per molecule of from about 2.5 to about 4 of which from about 40% to about 70% are conjugated, a density of from about 0.83 to about 0.93, an index of refraction of from about 1.47 to about 1.53, a. specific dispersion of from about 125 to about 175, a bromine number above 140, a maleic anhydride value of from about to about 90 and an acid'number below about 3. v

3. A surface active agent acidic dienophile selected from the group consisting of the mono and dibasic acidic compounds containing the reactive group: I

Jinan and (2) a polyolefmic, cyclic hydrocarbon fraction boiling in the range of from about 275 to I about 375 0., and having an average molecular weight of from about 225 to about 380, an average number of olefinic bonds per molecule of from about 2.5 to about 4 by which from about 40% to about are conjugated, a density of from about 0.83 to about 0.93, an index of refraction of from about 1.48 to about 1.50, a specific dispersion of from about 135 to about 145, a bromine number above 140, a maleic anhydride value of from about 45 to about and an acid number below about 3.

4. A surface active agent comprising the sodium salt derived from an adduct of methylacrylate and a, polyolefinic cyclic hydrocarbon fraction boiling within the range of from about 150 to about 450 0., having an average molecucomprising a water; soluble salt of an adduct of, (1) a monobasic' REFERENCES CITED The following references are of record in the file of this patent: Y

1 v UNITED STATES PATENTS Number Name Date 1,944,731 Diels et al Jan. 23, 1934 2,104,956 Stern et-al Jan. 11, 1938 2,230,005 Moser Jan. 28, 1941 2,352,606 Alder et a1 July 4, 1944 OTHER REFERENCES Kohler et al.: Journ. Am. Chem. Soc, vol. 61, pp, 1057-1061 (1929). 

1. A SURFACE ACTIVE AGENT COMPRISING A WATER SOLUBLE SALT OF AN ADDUCT OF, (1) AN ACIDIC DIENOPHILE SELECTED FROM THE GROUP CONSISTING OF THE MONO AND DIBASIC ACIDIC COMPOUNDS CONTAINING THE REACTIVE GROUP: 